DE2937831A1 - METHODS FOR THE HYDROXYLATION OF OLEFINICALLY UNSATURATED COMPOUNDS - Google Patents

Description

GERMAN GOLD AND SILVER SCHEIDEANSTALT FORMERLY ROESSLER Veissfrauenstrasse 9, 6000 Frankfurt 1

Henkel limited partnership based on shares Henkelstrasse 67, 4000 Düsseldorf

Process for hydroxylation olefinic unsaturated compounds

The invention relates to a process for the hydroxylation of olefinically unsaturated compounds with k to 36 carbon atoms and boiling points above 40 C by reaction with formic acid and hydrogen peroxide at elevated temperature and with thorough mixing and subsequent saponification of the formates contained.

It is already known to produce 1,2-diols by reaction of 1-olefins of 8 to 1Ö carbon atoms with formic acid and hydrogen peroxide at a temperature of 40 ⁰ C and with intimate rice Chung and subsequent hydrolysis of the formate formed (D. Swern et al. in J. Am. Chem. Soc. i> 8 (l ° 46), pages 1 504 to 1507). In the known process, the formic acid is used in amounts of about 9 to about 31 mol per mole of olefin, depending on the olefin used, and a hydrogen peroxide with a concentration of 25 × 6 percent by weight is used. The reaction requires one depending on the olefin used

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Response time between about 8 and about 2 hours. The crude 1,2-diols are obtained in the saponification of the diol monoformates formed in yields of 70 £ and above, but the yield of pure 1 ^ 2-diol is, depending on the olefin used, only between ^ 0 and 70% , .

The method according to the invention is now characterized in that that the formic acid is used in amounts of 2 to 6 mol per MoX double bond, hydrogen peroxide with a concentration from 35 to 98 percent by weight used and the implementation at a temperature between ^ O and 80 C.

Under these conditions, a reaction time of less than 7 hours, for example from 1 to 3 hours, to achieve a high conversion. The yield of pure Depending on the olefin used, diol is between about and about 92>.

The method according to the invention has about the same success applicable to linear olefins with a terminal or internal double bond and to cyclic olefins. Possibly The olefins to be used can also be branched and / or substituted by functional groups, for example carboxyl groups be. They can be used as pure substances or as mixtures of homologues or isomers. As with the erfindungsgeraässen If a pressureless procedure is preferred, the boiling points of the olefins to be used should be used above * tO C. That according to the invention is particularly suitable Process for the hydroxylation of relatively long-chain linear olefins with δ to 36 carbon atoms and a terminal or internal double bond.

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Monoolefins with a terminal double bond, so-called

χ -olefins, are usually obtained by the Ziegler ethylene oligomerization process. This mainly results in straight-chain olefins with an even carbon number. Up to a carbon number of about 10 they are commercially available as pure substances. The even longer-chain olefins are normally no longer obtained commercially as pure substances, but rather as olefin mixtures, for example in the chain length range C, C, _pK or C _nH

Monoolefins with an internal double bond are becoming technical obtained by dehydration of paraffin fractions and therefore normally make corresponding mixtures, e.g. with 11 to 14 carbon atoms, in which the double bonds are statistically distributed.

In the process according to the invention, the hydrogen peroxide can be used in a concentration of 35 to 98 percent by weight, preferably in a concentration

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be from 50 to 90 percent by weight employed · Advantageously, it is, if one does not become clogged from the beginning to the whole amount of hydrogen peroxide, but presents a mixture of olefin and the formic acid and the hydrogen peroxide but in the course of 1 to U metered hours. The hydrogen peroxide can be added continuously or in portions. For safety reasons, the gradual metering in of the hydrogen peroxide is particularly recommended when it is used in a higher concentration, for example a concentration of more than 50 percent by weight.

The reaction between the olefin and that formed in situ Performic acid is produced at a temperature between ^ o and

ο ο

ÖO C, preferably between 50 and 70 C, made.

To achieve a high yield, it is sufficient if the hydrogen peroxide is used in an amount of one mole per mole of double bond. Very high conversions, combined with good yields, can, however, be achieved if the hydrogen peroxide is used in a molar excess of 5 to 30 %, based on the double bond content of the olefin used.

The end of the reaction between the olefin and the in situ Performic acid formed is generally involved in the production of diols having fewer than 16 carbon atoms it can be seen that the reaction mixture becomes single-phase or at most still has a slight turbidity. If that Hydrogen peroxide is gradually added, this is it State usually reached immediately after the end of the dosing. In the production of diols with The reaction mixture remains 16 or more carbon atoms generally two-phase.

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The preferred way of working up in each case contributes to this difference Invoice! From single-phase systems it becomes more practical first the formic acid and the water are driven off at reduced pressure. Two-phase systems are advantageously a phase separation first subject. In both cases, the organic phase can then be used one or more times at an elevated temperature Stirred water and verden separately from the aqueous phase after cooling. No phase separation occurs because that formed diol is water-soluble to a considerable extent, so the diol is extracted with a suitable solvent, for example ethyl acetate. Particularly pure diols are obtained when treating the organic phase with alkaline substances. So can the organic phase first for about 15 minutes at an elevated temperature, for example at 70 C, with enough sodium hydroxide solution that the diol monoformates that are still present or that have been saponified by saponification formic acid released is neutralized. After separation of the aqueous phase or extraction of the formed Diols can then be washed one or more times with hot water until the crude diol or extract is free of alkali. The degree of purity of the so, if necessary after distilling off the extractant, obtained raw products is generally already so high that it can be used directly for a variety of conversions. If even higher degrees of purity are required in special cases, Can the crude diols easily by measures known per se, such as fractional distillation under reduced Pressure or urocrystallization from suitable solvents, for example from ethyl acetate, converted into pure products.

The economic advantages of the process according to the invention compared to the known by Swern et al. consist, among other things, that

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1. the required response time is significantly shorter;

2. The work-up of the crude reaction mixture as a result of the use of smaller amounts of formic acid and more concentrated ones Hydrogen peroxide is noticeably relieved, because only relatively small amounts of aqueous formic acid have to be removed from the system by distillation; and

3 · the yields of pure diol are considerably higher.

The use of additional solvents in the reaction between the olefin and the performic acid formed in situ is not necessary because at the reaction temperatures used both the olefins used and the crude reaction products are liquid. During the subsequent work-up of the crude reaction products, however, the use of additional solvents may be advantageous in cases in which the pure diols have a relatively high melting point. The crude reaction products can then be treated with solvents which have a high solubility for the diols formed, but only a low solubility in water and which are resistant to saponification. Suitable solvents are, for example, hydrocarbons or alcohols.

The method according to the invention is intended to be carried out by the following Examples are illustrated in more detail:

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- 8 - Example 1ί

In a k 1 stirred flask with attached reflux condenser and dropping funnel, 56Ο g rv-Cg olefin (5 mol) and 9 ^ 0 g 98 weight percent formic acid (20 mol) were mixed at a temperature of ^ Q C. Over the course of 2 hours, 3 ^ 0 g of 60 percent strength by weight hydrogen peroxide (6 mol) were metered in. After the addition was complete, the initially heterogeneous system had become single-phase. The volatile components (water and formic acid) were driven off in the course of half an hour in a water jet vacuum at a sump temperature of up to 110.degree. Then 2.6 l of water were added to the bottom product, the mixture was refluxed for 3 hours, cooled and separated from the aqueous phase. After drying in vacuo, 69Ο g of crude product were obtained which still had a monoformate content of 5 »7 percent by weight. The monoformate content was reduced to 0 percent by weight by stirring with 25 percent strength by weight sodium hydroxide solution (15 minutes at 70 ° C.). After the aqueous phase had been separated off, the crude diol was purified by distillation. The fraction passing over between 135 and 138 C (12 torr) weighed 635 g, "which corresponds to a yield of pure diol of 87.0 pounds of th"
point of the pure diol was 35

of pure diol of £ 87.0 corresponded to theory. The SchmelzZum Comparison can be made with the information from Swern et al. infer that from 06-Cg-olefin after a reaction time of 8 hours at a temperature of 4θ C and at a molar ratio of Olefin to formic acid of 1: 9 the pure diol with a melting point of 30-30.5 C in a yield of 58 $ of theory was obtained.

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Example 2:

Example I was repeated with 8 ^ 0 g of D ^ -C "-olefin (5 mol) and 291 g of 70 weight percent hydrogen peroxide (6 mol) at a reaction temperature of 55 ° C. The yield of pure diol was 90.5 ° j ° of theory, the melting point of the pure diol is 61.5 C.

For comparison, the information from Swern et al. infer that from a ^ -C -olefin after a reaction time of 2k hours at a temperature of ^ OC and with a molar ratio of olefin to formic acid of 1:13, the pure diol with a melting point of 60% of 40% of theory was obtained.

Diol with a melting point of 60-6 ° C in one yield

Example 3:

Example 1 was repeated with 1120 g of ct-C, -olefin (5 moles) and 2 ^ 0 g of 85 weight percent hydrogen peroxide (6 mol) at a reaction temperature of 60 C. The yield of pure diol was 92.3 $> according to theory, the melting point of the pure diol is 73.5 ° C.

For comparison, the information from Swern et al- shows that after a reaction time of 2k hours at a temperature of kO C and with a molar ratio of olefin to formic acid of 1:31, the pure diol is obtained _{from CX-C 1 / -olefin} a melting point of 75 ~ $ 58> of theory.

Diol with a melting point of 75 ~ 7 ^ C in one yield

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- 10 example kι

Analogously to Example 1, 175 6 of a technical olefin mixture with a chain length section of 11 to 14 carbon atoms, in which the double bonds were statistically distributed over the entire chain length, (~ 1 mol) and 188 g of 98 weight percent formic acid (no Moles) mixed. 6) g of 70 percent strength by weight hydrogen peroxide (1.25 mol) were metered in over the course of 1 hour. Then formic acid and water were driven off under reduced pressure and the distillation sump was stirred for 15 minutes at 70 ° C. with 165 g of a 25 percent strength by weight sodium hydroxide solution. The organic phase was separated off, washed twice more with 100 ml of water each time and finally subjected to distillation at 0.1 torr. The fraction passing between 110 and 1 ^ 0 C weighed 186 g, which corresponded to a yield of pure diol mixture of 89 ° p of theory. The melting range of the mixture was k ^ - 82 C.

Example 5:

252 g of OC-C "olefin (1 mol) and 280 g of 98 percent by weight formic acid (6 mol) were mixed in a 1 liter mixer at 60 C., and 52 g of 85 percent by weight hydrogen peroxide (1 _t 3 mol) offset. The system remained two-phase even after a reaction time of 1 hour and was therefore initially subjected to a phase separation. 130 g of aqueous phase with a formic acid content of about 80 percent by weight were separated off. From the organic phase were at reduced

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Pressure 130 g overhead product driven off. The resulting sump was mixed with benzene in a volume ratio of 1 to 2 and adjusted to neutrality at 70 ° C. with 20 percent strength by weight sodium hydroxide solution. After phase separation, the organic phase was washed twice with 100 ml of water each time and fractionally crystallized on cooling. The yield of Reindiol melting at 78.5 to 79, O ° C was 91.2 <£> theory.

Example 6:

The starting material is a commercially available C ^ Cp served _0-olefin., Had the following composition:

OL-C olefin approx. 1

Oc-C ₂₀ -01efin approx. 49

OC-C olefin approx. 42

OC-C ₂₂₊ -olefin approx. Ο

According to the above composition, the commercial product had an average molecular weight of 306 and a melting point of 32 C. In a 1 liter stirred apparatus, 306 g of olefin were mixed with 200 g of formic acid (98%; 6 mol) at 60 ° C. and mixed over the course of 1 hour 48 g of H ₃ O ₃ (85 g; 1.2 mol) were added. The system was stirred for a further hour at 60 ° C. and then separated from the aqueous phase. The excess amount of formic acid used was driven off from the remaining organic phase by distillation in vacuo (up to 90 ° C. at 12 torr). At 90-1OO ° C., the bottom product was then 150 g

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Sodium hydroxide solution (30 ^ ig) stirred and then (for better Separation of the two phases) with 600 ml of amyl alcohol. The aqueous phase could be drawn off while hot and the organic phase was washed with 100 ml of water. From the organic phase the solution mini Ctel (amyl alcohol) removed by distillation. The diol mixture remaining in the distillation residue weighed 3 ^ 0 g and had a residual olefin content of $ 5 and a freezing point of? 6 C.

Example ~ \

The starting product used was a cJ-olefin ingerai sch, which is commercially available under the name C " _{o +} -olefin. The mixture

should have a Q> ~ C_ _C -olefin content of 22 "ί and itself

2o

otherwise composed of C __ and even higher olefins. Based on the iodine number, an average molecular weight of ^ 453 was determined, which in turn has an average carbon number of approx. 32 corresponds.

1 mol of olefin mixture C "" ₊ was reacted and worked up according to Example 6, only the amount of 30% sodium hydroxide solution used being reduced to 120 g. KüO g of a diol mixture with a hestolefin content of 10 ^ and a solidification point of 90 C. were obtained.

At game b:

2 mol of Cyc3 open ten (136.2 g; bp_, = kk C) were mixed with 8 mol of formic acid (36b g; 90 / tig) and in a stirring apparatus (attached reflux condenser) with so-called "evaporative cooling"

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_{2.4 mol of H 2} O ₃ (96.3 g; & 5) were added over the course of 3 hours. The single-phase system was then stirred for a further 2 hours at 4 ° C. and then freed from formic acid and water of reaction by distillation (at the end of the Vacuum distillation reached a bottom temperature of approx. 90 ° C. at 12 torr).

The bottom product was treated with 2.2 mol of NaOH (08 g dissolved in 200 ml H2O) are added, cooled and at room temperature three times successively extracted with a total of 400 ml of ethyl acetate.

The combined extracts were distilled from ethyl acetate freed. In the distillation, cyclopentanediol remained as a residue (173 g), which corresponds to a yield of 0.5%.

The crude diol yield can be increased by further extractions will. By recrystallization or by distillation (Bp = 125-130 C) the crude diol can be purified further.

Example 9 '

1 mol of neohexene (3,3-dimethylbutene-1; 84 g; bp _g = 41 ° C.) was mixed with 4 mol of formic acid (184 g; 98%) and in a stirred apparatus with evaporative cooling over the course of 1.5 hours 1.2 mol HO (48 g; 85 % ± g) were added. The single-phase system was stirred at 50 ° C. for a further hour and then freed from 2.7 mol of formic acid by distillation. The bottom product was saponified with 1.3 mol of NaOH (= 52 g dissolved in 120 ml of water), cooled and extracted five times in succession with 100 ml of ethyl acetate each time. The ethyl acetate was distilled off from the combined extracts. The bottom product 94 g crude diol was obtained (ca. OEO ^ .ige yield) which by vacuum distillation - in pure Neohexandiol (solidification point = 3 ^ C) was transferred (Kp = 105 _ ¹¹ OC).

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Example 10:

1 mol of oleic acid (282 g) was treated with k mol of formic acid (98%;

164 g) and mixed at 50 ° C with 1.1 mol of HO (70 <£ ig; 54 g) in the course of one hour. After a further hour, the H 0 content in the single-phase system had dropped to 0.1 $, which was then freed from formic acid and water by distillation (up to 12 Torr and 90 ° C. in the sump). The bottom product was dissolved at −0 ° C. with 400 g of NaOH (25 "strength). The acid was liberated from the resulting Na salt of the dihydroxystearic acid by adding 100 g of HCl (conc.) In the molten state, the precipitated acid was separated from the aqueous phase and washed with 100 ml of H ₀ O. Dissolved water was removed by vacuum drying, leaving 301 g of crude dihydroxystearic acid, corresponding to a yield of about 95% crystallization (for example from ethyl acetate), the crude acid can be converted into a pure product (melting point 90/91 C).

1Ö. September 1979 Dr Sib-El

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Claims (2)

79 2Cri AO GERMAN GOLD AND SILVER SCHEIDEANSTALT FORMERLY ROESSLER
Weissfrauenstrasse 9, 6000 Frankfurt 1 Henkel limited partnership based on shares Henkelstrasse 6 ?, 4000 Düsseldorf Patent claims: "\ 1 · Process for the hydroxylation of olefinically unsaturated Compounds with k to 36 carbon atoms and boiling points above kO C by reaction with formic acid and hydrogen peroxide at elevated temperature and with thorough mixing and subsequent saponification of the formates contained, characterized in that
the formic acid in amounts of 2 to 6 moles per mole
Double bond is used, hydrogen peroxide with a concentration of 35 to 9% by weight is used and the reaction is carried out at a temperature between ^ O and ÖO ° C
undertakes. 2. The method according to claim 1, characterized in that a mixture of the olefin and the formic acid presents unrd the hydrogen peroxide in the course of 1 h to metered hours. 3. Process according to Claim 1 or 2, characterized in that the hydrogen peroxide is used in a molar excess of 5 to 30 <fo, based on the double bond content of the olefin used. 130021/0018